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United States Patent |
6,103,846
|
Willis
,   et al.
|
August 15, 2000
|
Process for making anionic polymeric di-and polyfunctional polymers
using protected functional initiators
Abstract
The preparation of di- or polyfunctional polymers by anionic polymerization
using functionalized initiators having the structure R.sup.1 R.sup.2
R.sup.3 Si--A--B, wherein each R is methyl and A is a hydrocarbon bridging
group containing from 1 to 25 carbon atoms, and B is an alkali metal, is
improved when polymerization occurs in the presence of a polymerization
termination inhibitor which is a metal alkyl which has been added at a
concentration to afford a molar ratio of the termination inhibitor to
living polymer chain ends of about 0.1:1 to about 10:1.
Inventors:
|
Willis; Carl Lesley (Houston, TX);
Bening; Robert Charles (Katy, TX);
Potter; Michael Wayne (Sugar Land, TX);
Haddix; Grant Wesley (Katy, TX);
Schisla; David Karl (Amsterdam, NL);
Semple; Thomas Carl (Friendswood, TX);
Goodwin; Daniel Earl (Katy, TX)
|
Assignee:
|
Shell Oil Company (Houston, TX)
|
Appl. No.:
|
305491 |
Filed:
|
May 5, 1999 |
Current U.S. Class: |
526/335; 526/176; 526/177; 526/178; 526/181 |
Intern'l Class: |
C08F 036/06; C08F 004/46 |
Field of Search: |
526/177,178,335,176,181
|
References Cited
U.S. Patent Documents
3631006 | Dec., 1971 | Hawkins | 526/178.
|
5331058 | Jul., 1994 | Shepherd et al. | 525/332.
|
5376745 | Dec., 1994 | Handlin, Jr. et al. | 526/178.
|
5416168 | May., 1995 | Willis et al. | 525/333.
|
Primary Examiner: Teskin; Fred
Attorney, Agent or Firm: Haas; Donald F.
Parent Case Text
This application claims the benefit of U.S. provisional application Ser.
No. 60/085,894, filed May 18, 1998, the entire disclosure of which is
hereby incorporated by reference.
Claims
We claim:
1. A process for making functionalized polymers, comprising the steps of:
(a) initiating polymerization of one or more anionically polymerizable
monomers with an initiator having the structure
##STR15##
wherein R.sup.1, R.sup.2, and R.sup.3 are independently selected from
saturated and unsaturated aliphatic and aromatic radicals, A is a
hydrocarbon bridging group containing from 1 to 25 carbon atoms, and B is
an alkali metal;
(b) polymerizing one or more anionically polymerizable monomers in the
presence of a polymerization termination inhibitor which is a metal alkyl;
and
(c) recovering a linear or branched polymer having one or more terminal
functional groups.
2. The process of claim 1 wherein the polymerization termination inhibitor
is present in a concentration such that the molar ratio of the inhibitor
to the living polymer chain ends is from 0.1 to 10.
3. The process of claim 2 wherein the ratio is 0.1 to 1.0.
4. The process of claim 1 wherein the polymerization termination inhibitor
is selected from the group consisting of trialkyl aluminum, dialkyl
magnesium, dialkyl zinc compounds, and combinations thereof.
5. The process of claim 4, wherein the polymerization termination inhibitor
is selected from the group consisting of triethylaluminum,
trimethylaluminum, diethylzinc, and ethylbutylmagnesium.
6. The process of claim 5 wherein the polymerization termination inhibitor
is triethylaluminum.
7. The process of claim 1 wherein the monomer is 1,3-butadiene.
8. The process of claim 1, wherein the alkali metal is lithium or sodium.
9. A functionalized polymer produced by a process comprising the steps of:
(a) initiating polymerization of 1,3-butadiene with an initiator having the
structure
##STR16##
wherein R.sup.1, R.sup.2, and R.sup.3 are independently selected from
saturated and unsaturated aliphatic and aromatic radicals, A is a
hydrocarbon bridging group containing from 1 to 25 carbon atoms, and B is
an alkali metal;
(b) polymerizing 1,3-butadiene in the presence of a polymerization
termination inhibitor which is a metal alkyl, wherein the molar ratio of
the inhibitor to the living polymer chain ends is from 0. 1 to 1.0; and
(c) recovering a linear or branched polymer having one or more terminal
functional groups.
10. The polymer of claim 9 wherein the molar ratio of the inhibitor to the
living polymer chain ends is from 0.5 to 1.0.
11. The polymer of claim 10 wherein the ratio is 0.5.
12. The polymer of claim 9 wherein the polymerization termination inhibitor
is selected from the group consisting of trialkyl aluminum, dialkyl
magnesium, dialkyl zinc compounds, and combinations thereof.
13. The polymer of claim 12 wherein the polymerization termination
inhibitor is selected from the group consisting of triethylaluminum,
trimethylaluminum, diethylzinc, and ethylbutylmagnesium.
14. The polymer of claim 13 wherein the inhibitor is triethylaluminum.
15. The reaction product of step (b) of claim 1.
16. The reaction product of claim 15 wherein the monomer is 1,3-butadiene.
17. The reaction product of claim 16 wherein the metal alkyl is
triethylaluminum.
18. The process of claim 9, wherein the alkali metal is lithium or sodium.
19. The reaction product of claim 9, wherein the metal alkyl is
triethylaluminum.
Description
FIELD OF THE INVENTION
This invention relates to anionic polymerization of unsaturated monomers to
make functionalized polymers useful in adhesives, sealants and coatings.
In particular, this invention relates to a process to make diol and polyol
polymers using a protected functional initiator and the diol polymers
resulting therefrom.
BACKGROUND OF THE INVENTION
Anionic polymerization of unsaturated monomers with lithium initiators,
such as sec-butyllithium, and hydrogenation of residual unsaturation has
been described in many references. Great Britain published patent
application 2,241,239 and related U.S. Pat. Nos. 5,331,058 and 5,362,699
describe a composition for an anionic protected functional initiator (PFI)
having the structure
##STR1##
wherein R.sup.1, R.sup.2, and R.sup.3 are independently selected from
saturated and unsaturated aliphatic and aromatic radicals, A is a
hydrocarbon bridging group containing from 1 to 25 carbon atoms and B is
an alkali metal, such as lithium. These documents disclose that a problem
with undesirable termination reactions can occur when using the PFI,
particularly if the radicals, R.sup.1, R.sup.2, and R.sup.3 are all methyl
or if together they contain less than 4 carbon atoms.
U.S. Pat. No. 5,416,168 describes a polymerization process using lithium
compounds having the structure:
##STR2##
wherein A" is cyclohexyl or --CR'R"--, wherein R' is a linear alkyl having
from 1 to 10 carbon atoms, and R" is hydrogen or a linear alkyl having
from 1 to 10 carbon atoms. This PFI also initiates polymerization of
anionic polymers at much higher polymerization temperatures than
previously known for PFIs and is cost effective to produce.
Unfortunately, even for the cost effective PFI of '168, it has been found
that in commercial applications where polymerization cycle times of two
hours or longer are possible, these initiators undergo undesirable
termination reactions. The results of these undesirable termination
reactions are varied and include (a) limiting the amount of polymer that
can be produced from a given amount of initiator, (b) broadening the
molecular weight distribution of the polymer, (c) limiting the ability to
make well defined block copolymers, and/or (d) limiting the ability for
postpolymerization chemistry, such as adding another functional site to
the living end of the polymer chain. Therefore it would be highly
desirable to develop a process which inhibits undesirable side reactions,
resulting in a higher functionality in the polymer product.
SUMMARY OF THE INVENTION
The present invention provides an improved process for making di- or
poly-functional polymers using polymerization initiators having the
structure:
##STR3##
wherein R.sup.1, R.sup.2, and R.sup.3 are independently selected from
saturated and unsaturated aliphatic and aromatic radicals, A is a
hydrocarbon bridging group containing from 1 to 25 carbon atoms, and B is
an alkali metal. One or more anionically polymerizable monomers especially
conjugated dienes, are polymerized in the presence of a polymerization
termination inhibitor that is a metal alkyl. Preferably, the metal alkyl
is selected from the group consisting of trialkyl aluminum, dialkyl
magnesium, and dialkyl zinc compounds.
In another embodiment of the invention, there is provided a functionalized
polymer produced when 1,3-butadiene is polymerized using a initiator
having the structure
##STR4##
wherein R.sup.1, R.sup.2, and R.sup.3 are independently selected from
saturated and unsaturated aliphatic and aromatic radicals, A is a
hydrocarbon bridging group containing from 1 to 25 carbon atoms, and B is
an alkali metal. The butadiene is polymerized in the presence of the
polymerization termination inhibitor described above.
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to functionalized polymers and processes for
inhibiting polymerization terminating side reactions that can occur when
protected functional initiators are used. Polymers which can be made
according the present invention are those made from any anionically
polymerizable monomer, especially including terminal functionalized
polydiene polymers, including random and block copolymers with styrene.
Styrene copolymers hereunder can be made in the same manner as the
polydiene polymers and can be random or block copolymers with dienes.
In general, the present invention will work to reduce or eliminate side
reactions when anionically polymerizing conjugated dienes or other
anionically polymerizable monomers using any protected functional
initiator having a reactive silicon center. Several PFIs have been
described in the art. For example, the production and use of PFIs having
the structure
##STR5##
wherein R.sup.1, R.sup.2, and R.sup.3 are independently selected from
saturated and unsaturated aliphatic and aromatic radicals, A is a
hydrocarbon bridging group containing from 1 to 25 carbon atoms, and B is
an alkali metal, preferably lithium, is described in Great Britain patent
application 2,241,239 and U.S. Pat. Nos. 5,331,058 and 5,362,699, which
are incorporated herein by reference. U.S. Pat. No. 5,321,148, which
description is incorporated by reference herein, describes the above PFI
as having R.sup.1, R.sup.2, and R.sup.3 independently selected from alkyl
groups containing 1 to 10 carbon atoms and aryl groups containing 6 to 10
carbon atoms, A selected from alkyl groups containing 2 to 8 carbon atoms
either straight chain or substituted by alkyl or aryl groups, and B as
lithium.
In a preferred embodiment, R.sup.1, R.sup.2 and R.sup.3 are each methyl;
the hydrocarbon bridging group has the structure CH.sub.2 --A"--CH.sub.2,
wherein A" is cyclohexyl or --CR'R"--, R' is a linear alkyl having from 1
to 10 carbon atoms and R" is hydrogen or a linear alkyl having from 1 to
10 carbon atoms; and B is lithium, resulting in the structure
##STR6##
This is described in U.S. Pat. No. 5,416,168, which description is
incorporated herein by reference. The initiator of structure (2) has been
used to prepare polymers of butadiene which have a uniform distribution of
1,2-addition when the amount of 1,2-addition is between 5 and 95% w, more
preferably between 30 to 70% w.
The alkali metal initiator process is well known. U.S. Pat. Nos. 4,039,593
and Re. 27,145, which descriptions are incorporated herein by reference,
describe the process for lithium initiators. Typical living polymer
structures that can be made with alkali metal initiators:
##STR7##
wherein B represents polymerized units of one or more anionically
polymerizable monomers, especially conjugated diene hydrocarbons, A
represents polymerized units of one or more vinyl aromatic compounds, B/A
represents random polymerized units of the conjugated diene hydrocarbons
and the vinyl aromatic monomers, M is an alkali metal, and X is the
residue of the initiator. The living polymers are terminated as linear
polymers, coupled to form branched polymers, or capped to form additional
functional groups by conventional means such as addition of methanol,
silicon tetrachloride, divinylbenzene, or ethylene oxide.
Unfortunately, the PFI initiators undergo undesirable termination, or
"side" reactions. Great Britain patent application 2,241,239 warned of
reactivity of the siloxy group and suggested that the radicals R.sup.1,
R.sup.2, and R.sup.3 not all be methyl, and preferably that one be aryl,
and that the total carbon atoms in the radicals be at least 4, preferably
5. It has now been discovered that the adverse side reactions involve a
reaction of the living, C--M end of the anionic polymer chain with the
protected, R.sup.1 R.sup.2 R.sup.3 SiOC, end. This side reaction, which
appears to occur a little over 10% of the time, results in the transfer of
the alkali metal moiety from the growing end of the polymer chain to the
inactive, protected functional group end of the molecule. For example,
when a PFI of Structure (2) is used, in some of the molecules the desired
structure of the living polymerization product
##STR8##
In the undesired structures, the living polymer C--Li end's reactivity is
terminated, making the molecule inert to (a) further polymerization and
(b) postpolymerization reactions, such as capping with ethylene oxide.
Loss of activity in further polymerization affects the cost effectiveness
of the initiator, limits the initiator's effectiveness in making block
copolymers, and tends to broaden the molecular weight distribution of the
product. Loss of postpolymerization reaction capability means that desired
reactions, such as reacting the polymer chain with ethylene oxide to make
a difunctional telechelic polymer or reacting with a coupling agent to
make a linked polymer having functional groups on the ends of the
molecules, become limited. Thus the polymer mixture becomes one containing
monofunctional impurity, a structural phenomenon of great commercial
disadvantage compared to difunctional polymers.
The process of the present invention employs termination inhibitors that
inhibit the alkali metal-silicon attack. This inhibition of termination
seems to occur as a result of the living polymer chain end reacting
reversibly with the metal alkyl inhibitor to form an "ate complex." An
illustrative example of this concept is shown below for the case where
triethylaluminum is the metal alkyl inhibitor and butadiene is the
anionically polymerizable monomer. The "ate complex" appears to be less
reactive with the Si--O bond on the protected end of the polymer chain.
This may, at least in part, be due to the increased steric bulk of the
"ate complex."
##STR9##
The C--Li center on an uninhibited, living chain end is smaller and
therefore more prone to the undesired side reaction with the Si--O bond of
a protected polymer chain end than is the large, bulky end of an "ate
complex." It is likely the case that the maximum level of inhibition is
achieved when the inhibitor is present in a concentration equal to that of
living polymer chain ends (Metal Alkyl/C--Li Center=1(mol/mol)). For the
purpose of controlling other aspects of the polymerization reaction, such
as the polymerization rate, it may be desirable to use less of the
inhibitor. The lower limit on an effective amount of the inhibitor would
best be determined by experiment. It is unlikely that levels below one
inhibitor per 10 C--Li chain ends (Metal Alkyl/C--Li Center>0. 1) give a
measurable level of inhibition of the side reaction with the Si--O
centers. Levels of inhibitor that are in molar excess of the living
polymer chain ends, C--Li centers, are expected to be effective inhibitors
of the undesired side reaction but will not be markedly better than a
molar ratio of 1:1. As excess levels of inhibitor are not expected to
improve performance, they will add unnecessarily to the cost of the
process. For this reason, lower levels of the inhibitor reagent are
preferred. The inhibitor is used in molar ratios relative to the living
polymer chain ends of from 0.1 to 10, more preferably from 0.1 to 1, most
preferably from 0.5 to 1.
The inhibitor selected should be a metal alkyl. Preferably, the metal alkyl
is selected from the group consisting of trialkyl aluminum, dialkyl
magnesium, trialkyl boron and dialkyl zinc compounds. Preferred
trialkylaluminum compounds are triethylaluminum, trimethylaluminum,
tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,
tri-n-hexylaluminum, and trioctylaluminum because these reagents are
readily available in commercial quantities. Triethylaluminum is most
preferred as it is least expensive on a molar basis. Preferred
dialkylmagnesium compounds are butylethylmagnesium, di-n-butylmagnesium,
and di-n-hexylmagnesium because these reagents are readily available in
commercial quantitites. Preferred dialkyzinc compounds are dimethylzinc,
diethylzinc, di-n-propylzinc, diisobutylzinc, and di-n-butylzinc because
these reagents are readily available in commercial quantities.
A polymerization process using these termination inhibitors undergoes less
of the undesired termination reactions than analogous polymerization
processes that do not use the polymerization termination inhibitors. The
polymerization process is thus more efficient because a greater number of
polymerization sites remain active throughout the polymerization. The
polymer produced also has a narrower molecular weight distribution and a
higher degree of di- or poly-functionality from the improved reactivity in
end capping or coupling reactions.
Great Britain patent application 2,241,239 suggested that, in order to
reduce reactivity of the siloxy group, polymerization temperature be
controlled between -30.degree. C. and +30.degree. C. Unfortunately, for
commercial applications such polymerization temperatures are cost
prohibitive, as the reagents must be cooled for such an exothermic
reaction. Also, the polymerization time at the lower temperatures is much
longer than is commercially feasible. PFIs are very active at room
temperature and it has been found that polymerization is preferably
initiated at a temperature from 15.degree. C. to 60.degree. C., most
preferably from 30.degree. C. to 40.degree. C. It is generally advisable
to keep the polymerization temperature below about 100.degree. C. or side
reactions that change microstructure and limit capping efficiency may
become important. Polymerizations can be carried out over a range of
solids levels, preferably from about 5% w to about 80% w polymer, most
preferably from about 10% w to about 40% w.
When the conjugated diene is 1,3-butadiene and when the conjugated diene
polymer will be hydrogenated, the anionic polymerization of the conjugated
diene hydrocarbons is typically controlled with high concentrations of
structure modifiers such as diethyl ether to obtain the desired amount of
1,2-addition. As described in Re 27,145 which is incorporated by reference
herein, the level of 1,2-addition of a butadiene polymer or copolymer can
greatly affect the clarity, rheology, and elastomeric properties of the
polymer after hydrogenation. It is desired that the modifier result in a
polybutadiene with about 40% to 70% vinyl content. To accomplish this it
is typical to use a diethyl ether: chain end ratio of greater than 1:1
mol/mol.
Polymerization may take place using the typical batch process. Certain
advantages have been found, however, when a continuously stirred tank
reactor or other continuous flow reactor, such as a plug flow or multiple
stage flow reactor, is used, particularly if the conjugated diene is
butadiene. As mentioned previously, a preferred temperature for
polymerization is from 30.degree. C. to 40.degree. C. In a
batch/semi-batch process, the PFIs are slow to initiate in this
temperature range and may never completely initiate. Also, heat released
by the exothermic polymerization reaction becomes concentrated into
certain regions of the batch cycle, making temperature control difficult.
The use of a continuous flow reactor, such as a continuously stirred tank
reactor, helps to reduce the impact of these problems. Residence time may
be substantially reduced (85% to 90% reduction), further reducing the
incidence of undesirable endcaps, without loss of PFI conversion because
temperatures may be increased. The continuously stirring or flow also
helps evenly distribute the heat load, reducing the required heat removal
duties of the batch polymerization reactor.
Anionic polymerization is often terminated by addition of water to remove
the lithium as lithium hydroxide (LiOH) or by addition of an alcohol (ROH)
to remove the lithium as a lithium alkoxide (LiOR). Polymers prepared from
initiators of the present invention and terminated in this way will be
mono-hydroxyl functional materials (mono-ols) after removal of the
trimethylsilyl ether-protecting group. To prepare polymers having an
additional hydroxyl terminal functional groups, the living polymer chains
are preferably terminated by addition of ethylene oxide, oxetane, or
2,2-dimethyloxetane. To prepare polymers having an additional terminal
functional group that is carboxyl, the living polymer chains are
preferably terminated by addition of carbon dioxide. To prepare polymers
having an additional terminal functional group that is phenolic, the
living polymer chains are preferably terminated by addition of a protected
hydroxystyrene monomer. To prepare polymers having an additional terminal
functional group that is epoxy, the living polymer chains are preferably
terminated by addition of ethylene oxide to make the lithium alkoxide
(OLi) chain end which is then reacted with epichlorohydrin to make the
glycidol ether epoxide. To prepare polymers having an additional terminal
functional group that is an amine, the living polymer chains are
preferably terminated by addition of an aziridine reagent such as that
listed in U.S. Pat. No. 4,791,174 which is herein incorporated by
reference.
The most preferred process polymerizes 1,3-butadiene at 5% to 30% solids
using an initiator having the following structure:
##STR10##
(3-lithio-2,2-dimethyl-1-trimethylsilyloxypropane). The 1,3-butadiene is
added either in batch or by programmed addition of monomer, depending upon
the cooling capability of the reactor. Polymerization occurs in the
presence of triethylaluminum, a polymerization termination inhibitor which
is added such that the molar ratio of triethylaluminum to living polymer
chain ends is from 0.1 to 10, preferably 0.1 to 1, more preferably from
0.5 to 1. The polymerization reaction time is sufficient to achieve at
least 80% conversion of the conjugated diene monomer to polybutadiene.
More preferably 90% conversion is achieved. Most preferable is conversion
in excess of 95%.
After polymerization of the desired amount of 1,3-butadiene, the living
polymer is capped with ethylene oxide and reacted with methanol to give a
terminal primary alcohol functional group on one end of the polymer chain.
The protected functional initiator on the other end of the polymer chain
is then deprotected. For example, the silyl ether group on the other end
of the chain is then converted to a primary, neopentyl-type hydroxyl group
by reaction with aqueous acid or aqueous base affording a telechelic
dihydroxy polymer product.
Hydrogenation of at least 90%, preferably at least 95%, of the unsaturation
in low molecular weight butadiene polymers is achieved with nickel
catalyst as described in U.S. Pat. Nos. 27,145, 4,970,254, and 5,166,277
which are incorporated by reference herein.
After polymerization and, optionally, hydrogenation and washing of the
polymer, the trimethylsilyl ether group at the front of the polymer chain
is removed to generate the desired primary, neopentyl-type hydroxyl
functional group. This step is often referred to as deprotection. A
variety of processes for removal of the silyl protecting group are known;
for a review, see T. W. Greene, "Protective Groups in Organic Synthesis",
J. Wiley and Sons, New York, 1981. Deprotection preferably involves easily
handled, relatively low toxicity, inexpensive reagents and mild, low cost
process conditions. In a preferred process, the trimethylsilyl ether group
is removed after hydrogenation and during the aqueous acid wash for
removal of the spent Ni/Al hydrogenation catalyst. This technique avoids
the cost associated with a separate process step for deprotection. For the
preparation of an unsaturated polymer where hydrogenation catalyst
extraction is not required, contacting the polymer cement with a dilute
aqueous acid or dilute aqueous base solution is preferred for
deprotection.
A composition of the instant invention may contain plasticizers, such as
rubber extending plasticizers, or compounding oils or organic or inorganic
pigments and dyes. Rubber compounding oils are well-known in the art and
include both high saturates content oils and high aromatics content oils.
Preferred plasticizers are highly saturated oils, e.g. TUFFLO.RTM. 6056
and 6204 oil made by Arco and process oils, e.g. SHELLFLEX.RTM. 371 oil
made by Shell. The amounts of rubber compounding oil employed in the
invention composition can vary from 0 to about 500 phr, preferably between
about 0 to about 100 phr, and most preferably between about 0 and about 60
phr. Phr means "parts per hundred rubber" which is parts by weight per 100
parts by weight of polymer wherein the polymer is referred to as the
"rubber".
Optional components of the present invention are stabilizers that inhibit
or retard heat degradation, oxidation, skin formation and color formation.
Stabilizers are typically added to the commercially available compounds in
order to protect the polymers against heat degradation and oxidation
during the preparation, use and high temperature storage of the
composition.
Various types of fillers and pigments can be included in the coating or
sealant formulation. This is especially true for exterior coatings or
sealants in which fillers are added not only to create the desired appeal
but also to improve the performance of the coatings or sealant such as its
weather-ability. A wide variety of fillers can be used. Suitable fillers
include calcium carbonate, clays, talcs, silica, zinc oxide, titanium
dioxide and the like. The amount of filler usually is in the range of 0 to
about 65% w based on the solvent free portion of the formulation depending
on the type of filler used and the application for which the coating or
sealant is intended. An especially preferred filler is titanium dioxide.
The dihydroxylated conjugated diene polymers of the present invention may
also be blended with other polymers to improve their impact strength
and/or flexibility. Such polymers are generally condensation polymers
including polyamides, polyurethanes, vinyl alcohol polymers, vinyl ester
polymers, polysulfones, polycarbonates and polyesters, including
polyacetones, polyalkylene arylates, including polyalkylene
terephthalates, having a structure formed by polycondensation of a
dicarboxylic acid with a glycol. The blends may be made in the reactor or
in a post compounding step.
The conjugated diene polymers produced as described herein have the
conventional utilities for terminally functionalized polymers such as
forming adhesives, coatings, and sealants. Additionally, the polymers may
be used to modify polyurethanes, polyesters, polyamides, polycarbonates,
and epoxy resins. The preferred polymers of the present invention are
useful in adhesives (including pressure sensitive adhesives, contact
adhesives, laminating adhesives and assembly adhesives), sealants (such as
urethane architectural sealants, etc.), coatings (such as topcoats for
automotive, epoxy primers for metal, polyester coil coatings, alkyd
maintenance coatings, etc.), films (such as those requiring heat and
solvent resistance), molded and extruded thermoplastic and thermoset parts
(for example thermoplastic injection molded polyurethane rollers or
reaction injection molded thermoset auto bumper, facie, etc.).
The present invention is further described by the following examples. The
examples are not intended to limit the present invention to specific
embodiments.
EXAMPLES
EXAMPLE 1
##STR11##
In a stainless steel autoclave, sec-butyllithium (s-BuLi) (67g of a 12%
solution in cyclohexane, 0.125 mol) was reacted with 1,3-butadiene (Bd)
(400g, 7.4 mol) to make a living mono-initiated polymer. Polymerization
was in a cyclohexane/diethyl ether mixture (90/10 (wt/wt)). At full
conversion, the mixture contained about 20% wt of a living polybutadiene.
After polymerization, Et.sub.3 Al (TEA) (87 g of a 1M solution in hexane,
0.125 mol) was added to make TEA:C--Li=1:1 (mol:mol). The purpose of the
added TEA was to inhibit the rate of addition of the chain ends to the
added Si--O moiety. Hexamethyldisiloxane (HMDS)(20.2 g, 0.125 mol) was
added as a model for the chain end of a Protected Functional Initiator
(PFI) reagent. Reaction proceeded for 3 hours at 57.degree. C. Aliquots
were taken over the course of the reaction, quenched, and analyzed by
H--NMR with the following results:
______________________________________
Time % Chain Ends With Me.sub.3 Si Cap (mol %)
______________________________________
0 1.7
5 1.7
15 1.8
20 1.8
30 1.8
60 2.2
120 2.5
180 3.0
______________________________________
The undesired side reaction, capping the living polymer chain end with the
added silicon reaction, was slow in the presence of the termination
inhibitor, TEA. The capping level increased by only 1.3% over the course
of 3 hours at 57.degree. C. The sample taken at 0 time (before the
addition of the HMDS reagent) had Si caps already which was due to
contamination in the reactor.
COMPARATIVE EXAMPLE 1
##STR12##
This experiment was conducted in the same manner as Example 1 with the
exception that no TEA was added to inhibit the Si capping reaction. The
living polymer concentration was the same (20% wt polymer) and the living
polymer chain end concentration was the same. The solvent mixture was the
same (cyclohexane/diethyl ether (90/10 (wt/wt)). The living polymer was
treated with HMDS at a level such that the HMDS:C--Li=1:1. This is the
same as had been used in Example 1. Reaction with HMDS was at
53-58.degree. C. The important difference between this experiment and that
outline in Experiment 1 was that no TEA was added before the HMDS reagent
was added. After 2 hours of reaction, 16.4% of the chain ends had Me.sub.3
Si caps. This indicates that there had been a high level of reaction with
HMDS, the undesired side reaction.
EXAMPLE 2
##STR13##
A polymer was prepared using 3-lithio-2,2-dimethyl-1-trimethylsiloxypropane
(85 g of 12.2% (wt) solution in cyclohexane, 0.0625 mol), and
1,3-butadiene (200g, 3.7 mol). Polymerization in a cyclohexane/diethyl
ether mixture (90/10 (wt/wt)) at about 30.degree. C. gave about 10%wt
polymer at complete conversion. After 12 min of polymerization, about 1
half-life, TEA (43.2g of a 1M solution in hexane, 0.062 mol) (TEA:C--Li=1
(mol:mol)) was added to inhibit the reaction of the living polymer chain
end with the Me.sub.3 SiO-end of the polymer chain. Aliquots were taken at
timed intervals after the addition of TEA, quenched, and analyzed by
H--NMR with the following results:
______________________________________
Time % Chain Ends With Me.sub.3 Si Cap (mol %)
______________________________________
0 2.0
13 3.0
27 3.0
37 3.0
74 5.0
98 6.0
125 5.0
______________________________________
After reacting for over 2 hours at 30.degree. C. in the presence of TEA,
the Si capping level had increased by only about 3 to 4 mol %.
COMPARATIVE EXAMPLE 2
##STR14##
An experiment was conducted at the same conditions as Example 2 with the
exception that none of the Si capping inhibitor reagent, TEA, was added.
After two hours of reaction at a temperature of about 30.degree. C., the
Me.sub.3 Si capping level was 14%. This is much higher than had been
observed in the presence of the inhibitor, TEA.
COMPARATIVE EXAMPLE 3
An experiment was conducted at the same conditions as Example 2 with the
exception that none of the Si capping inhibitor reagent, TEA, was added.
After two hours of reaction, the Me.sub.3 Si capping level was 15.7%. This
is much higher than had been observed in the presence of the inhibitor,
TEA.
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